Method for preparing lithium iron phosphate nanopowder

ABSTRACT

The present invention relates to a method for preparing a lithium iron phosphate nanopowder, including the steps of (a) preparing a mixture solution by adding a lithium precursor, an iron precursor and a phosphorus precursor in a glycerol solvent, and (b) putting the mixture solution into a reactor and heating to prepare the lithium iron phosphate nanopowder under pressure conditions of 10 bar to 100 bar, and a lithium iron phosphate nanopowder prepared by the method. When compared to a common hydrothermal synthesis method and a supercritical hydrothermal synthesis method, a reaction may be performed under a relatively lower pressure. When compared to a common glycothermal synthesis method, a lithium iron phosphate nanopowder having effectively controlled particle size and particle size distribution may be easily prepared.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a method for preparing a lithium iron phosphate nanopowder.

2. Description of the Related Art

As technical development and consumption of mobile devices increase, the demand for secondary batteries as energy sources is suddenly increasing. Among such secondary batteries, lithium secondary batteries having high energy density and voltage, a long life cycle, and a low self-discharge rate are being commercialized and widely used.

Common lithium secondary batteries use lithium cobalt oxide (LiCoO₂) as the main component of a cathode active material. However, since the cobalt oxide containing lithium is unstable and expensive, the mass production of lithium secondary batteries including thereof is difficult.

Recently, lithium iron phosphate (LiFePO₄) compound having a voltage against lithium of ˜3.5 V, a high volume density of 3.6 g/cm³, and a theoretical capacity of 170 mAh/g, as well as good stability at high temperature, and being cheap when compared to lithium cobalt oxide, is being viewed as a suitable cathode active material for a lithium secondary battery.

As methods for preparing the lithium iron phosphate compound, a solid-state reaction method or a liquid-state reaction method such as a hydrothermal synthesis method and a supercritical hydrothermal synthesis is known. Recently, a glycothermal synthesis method is using a non-aqueous solution such as ethylene glycol or diethylene glycol as a reaction solvent has been developed. According to the hydrothermal synthesis method and the supercritical hydrothermal synthesis method, the preparation of the lithium iron phosphate nanopowder is performed under high temperature and high pressure conditions, giving rise to safety concerns. In addition, according to the glycothermal synthesis method, the control of the particle size and the particle size distribution of the lithium iron phosphate nanopowder may be difficult.

SUMMARY OF THE INVENTION

An aspect of the present invention provides a method for preparing a lithium iron phosphate nanopowder by a glycothermal synthesis method and using a novel reaction solvent to resolve the above-described limitations, by which a reaction may be performed under relatively low pressure conditions when compared to a common hydrothermal synthesis method and a supercritical hydrothermal synthesis method, and a particle size and a particle size distribution may be effectively controlled when compared to a common glycothermal synthesis method.

According to an aspect of the present invention, there is provided a method for preparing a lithium iron phosphate nanopowder including (a) preparing a mixture solution by adding a lithium precursor, an iron precursor and a phosphorus precursor in a glycerol solvent, and (b) putting the reaction mixture into a reactor and heating to form a lithium iron phosphate nanopowder under pressure conditions of 10 bar to 100 bar.

According to another aspect of the present invention, there is provided a lithium iron phosphate nanopowder prepared by the method, and a cathode active material including the same.

According to still another aspect of the present invention, there is provided a cathode including the cathode active material and a lithium secondary battery including the cathode.

According to the method for preparing a lithium iron phosphate nanopowder, a reaction may be performed under relatively lower pressure conditions when compared to a common hydrothermal synthesis method and a supercritical hydrothermal synthesis method, such that process safety and economic feasibility may be secured. In addition, a lithium iron phosphate nanopowder of which particle size and particle size distribution are effectively controlled when compared to a common glycothermal synthesis method may be easily prepared.

A lithium secondary battery including the lithium iron phosphate nanopowder thus prepared as a cathode active material has good capacity and stability.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an X-ray diffraction (XRD) pattern of a lithium iron phosphate nanopowder prepared according to an embodiment of the present invention (Example 1); and

FIG. 2 is a photographic image of a scanning electron microscope (SEM) of a lithium iron phosphate nanopowder prepared according to an embodiment of the present invention (Example 1).

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Exemplary embodiments of the present invention will now be described in detail.

In the present invention, a method for preparing a lithium iron phosphate nanopowder by means of a glycothermal method which is one liquid-state reaction method is provided. Particularly, a reaction may be performed under relatively low pressure conditions when compared to a common hydrothermal synthesis method and a supercritical hydrothermal synthesis method by using glycerol as a reaction solvent, and a lithium iron phosphate nanopowder having an effectively controlled particle size and particle size distribution when compared to a common glycothermal synthesis method may be prepared.

In an embodiment for attaining an aspect of the invention, a method for preparing a lithium iron phosphate nanopowder including (a) preparing a mixture solution by adding a lithium precursor, an iron precursor and a phosphorus precursor in a glycerol solvent, and (b) putting the reaction mixture into a reactor and heating to form a lithium iron phosphate nanopowder under the pressure conditions of 10 bar to 100 bar, is provided.

In another embodiment of the present invention, the method may further include (c) heat treating the lithium iron phosphate nanopowder thus prepared to form a coating layer on a portion or the whole of the surface of the individual particle of the nanopowder.

First, a lithium precursor, an iron precursor, and a phosphorus precursor are prepared and added in a glycerol reaction solvent to prepare a homogeneous mixture solution (Step (a)).

The lithium precursor thus added may be at least one selected from the group consisting of lithium acetate dihydrate (CH₃COOLi.2H₂O), lithium hydroxide monohydrate (LiOH.H₂O), lithium hydroxide (LiOH), lithium carbonate (Li₂CO₃), lithium phosphate (Li₃PO₄), lithium phosphate dodecahydrate (Li₃PO₄.12H₂O), lithium oxalate (Li₂C₂O₄), and a mixture thereof.

The iron precursor added may be at least one selected from the group consisting of iron citrate (FeC₆H₅O₇), iron citrate hydrate (FeC₆H_(S)O₇.nH₂O), ferrous sulfate heptahydrate (FeSO₄.7H₂O), iron(II) oxalate dihydrate (FeC₂O₄.2H₂O), iron acetyl acetonate (Fe(C₅H₇O₂)₃), iron phosphate dihydrate (FePO₄.2H₂O), ferric hydroxide (FeO(OH)), and a mixture thereof.

The phosphorus precursor added may be at least one selected from the group consisting of tri-ammonium phosphate trihydrate ((NH₄)₃PO₄.3H₂O), ammonium phosphate ((NH₄)₂HPO₄), ammonium dihydrogen phosphate (NH₄H₂PO₄), phosphoric acid (H₃PO₄), and a mixture thereof.

Meanwhile, the mixing ratio of the lithium precursor, the iron precursor and the phosphorus precursor during the forming of the mixture solution is not specifically limited, and may be, for example, 0.1-10:1:0.1-10 by the molar ratio.

In addition, the iron precursor may be added from about 0.005 to about 1 parts by weight based on 1 part by weight of the glycerol reaction solvent, and the lithium precursor and the phosphorus precursor may be added by corresponding molar ratios considering the amount of the iron precursor.

Meanwhile, a stirring step may be further conducted during preparing the mixture solution so that the lithium precursor, the iron precursor and the phosphorus precursor may be homogeneously dispersed in the glycerol reaction solvent.

The reaction solvent maybe glycerol which is a non-aqueous solvent and has a relatively high boiling point.

The boiling point of the glycerol is about 290° C.

The lithium iron phosphate nanopowder was verified to be synthesized at temperature conditions of at least about 150° C.

That is, when the above-described reaction solvent is used for preparing the lithium iron phosphate nanopowder, the reaction may be performed at a temperature less than equal to the boiling point of the reaction solvent, and the vaporization degree of the reaction solvent may decrease. Thus, the pressure increase due to vaporization of solvent during the performing of the reaction may be significantly suppressed when compared to a common hydrothermal synthesis method. Therefore, safety throughout the process maybe improved.

In addition, since the above described glycerol reaction solvent is non-aqueous, the problem of iron oxidation may be resolved without using a separate reducing agent.

Then, the mixture solution was put into the reactor and heated to prepare the lithium iron phosphate powder under the pressure conditions of 10 bar to 100 bar (Step (b)).

The reactor is a pressure-resistant vessel that may endure the pressure conditions from 10 bar to 100 bar, and may be a generally used reactor in a glycothermal synthesis method. The material of the reactor may be a low carbon steel, an alloy steel of chromium, nickel or molybdenum, etc. In an embodiment of the present invention, the reactor may be an autoclave.

Meanwhile, the above Step (b) may be performed at the temperature range of at least 150° C. which is the minimum temperature for synthesizing the lithium iron phosphate nanopowder, and at a temperature range less than or equal to the boiling point of the reaction solvent used.

Since the reaction solvent used in the present invention is glycerol, the above Step (b) may be performed at about 150° C. to about 290° C.

That is, the reaction is performed at a temperature between the minimum temperature for synthesizing the lithium iron phosphate nanopowder and a temperature less than equal to the boiling point of the reaction solvent, and the vaporization of the reaction solvent is slowed down. Thus, the pressure increase of the reactor due to the vaporization of the solvent may be suppressed when compared to a common hydrothermal synthesis method, etc.

Meanwhile, the pressure in the reactor during the performing of the above Step (b) is in the range of 10 bar to 100 bar. The pressure is relatively low when compared to that of a common hydrothermal synthesis method (at least about 100 bar) or of a supercritical hydrothermal synthesis method (at least about 220 bar), which provides an even better effect when considering process safety and economic feasibility.

The processing time of the above Step (b) may be changed according to the reaction solvent used and the reaction temperature.

In an embodiment of the present invention, the above Step (b) may be conducted at a temperature range of 150° C. to 290° C. for 1 to 48 hours, and more particularly, may be conducted at a temperature range of 180° C. to 290° C. for 1 to 24 hours.

When Step (b) is finished, lithium iron phosphate nanopowder particle may be synthesized, and a washing step and a drying step for recovering the synthesized lithium iron phosphate nanopowder particle in Step (b) may be conducted sequentially.

The washing method in the washing step is not specifically limited, and may be conducted sequentially by using acetone and methanol.

The drying method in the drying step is not specifically limited, and may be conducted at a temperature range of 20° C. to 160° C. for 2 to 40 hours.

The lithium iron phosphate nanopowder synthesized through the processes maybe heat treated to form a coating layer on a portion or the whole of the surface of the individual particle of the powder (Step (c)).

The above Step (c) may be performed through heat treating. The heat treating is not specifically limited and may be conducted by heating to a temperature range of 400° C. to 900° C., for example. Through the heat treating, a carbon coating layer or a coating layer composed of a glassy lithium compound may be formed on a portion or the whole of the surface of the particle.

When the coating layer is the carbon coating layer, the precursor of the coating layer maybe the reaction solvent remaining on the surface of the particle after use. Particularly, the glycerol used as the solvent may remain on the surface of the particle after conducting the drying step and may be carbonized during the heat treatment at a temperature range of 400° C. to 900° C., thereby forming the carbon coating layer on the surface of the particle.

A separate organic compound may be used as the precursor of the carbon coating layer, and the addition step of the separate organic compound for forming the carbon coating layer on the surface of the lithium iron phosphate nanopowder particle is not specifically limited.

In an embodiment of the present invention, the organic compound may be mixed with the solvent together with the lithium precursor, the iron precursor and the phosphorus precursor and react to form the carbon coating layer on the surface of the particle during the forming of the lithium iron phosphate particle.

In another embodiment, the lithium precursor, the iron precursor and the phosphorus precursor are mixed with the solvent and react to form the lithium iron phosphate particle, and then, the organic compound is added, mixed and heat treated to form the carbon coating layer on the surface of the particle.

In further another embodiment, the lithium precursor, the iron precursor and the phosphorus precursor are mixed with the solvent and react to form the lithium iron phosphate particle, and washing and drying processes are performed. Thereafter, the organic compound is added, mixed and heat treated to form the carbon coating layer on the surface of the particle.

The organic compound is not specifically limited, and may be at least one selected from the group consisting of glucose, sucrose, galactose, fructose, lactose, starch, mannose, ribose, aldohexose, ketohexose, and a mixture thereof.

When the coating layer is the glassy lithium compound coating layer, the coating layer is not specifically limited, and may be, for example, a lithium phosphate-based amorphous coating layer. In this case, the precursor material may be a lithium precursor and a phosphorus precursor, and may be an additional lithium compound and phosphorus compound.

The thickness of the carbon coating layer or the glassy lithium compound coating layer formed on the surface of the particle in this step is not specifically limited, and may be, for example, less than or equal to 10 nm.

Since the lithium iron phosphate powder has low electric conductivity, the electric conductivity of the lithium iron phosphate powder may be improved by forming the carbon coating layer or the coating layer including the glassy lithium compound on a portion of or the whole surface of the minute lithium iron phosphate powder particle thus prepared.

The lithium iron phosphate nanopowder particle prepared through the series of the above-described steps may have an olivine structure.

The particle size and the particle size distribution of the particle may be controlled by changing the lithium precursor, the iron precursor, or the phosphorus precursor, or regulating processing variables such as reaction temperature and reaction time, etc. For example, the size of the lithium iron phosphate particle may be decreased when using lithium acetate as the lithium precursor.

In addition, the size of the lithium iron phosphate particle may increase when the reaction temperature is elevated or the reaction time is prolonged.

The particle size (Hereinafter will be referred to as particle diameter) of the lithium iron phosphate nanopowder prepared through the above-described process is not specifically limited, and may be, for example, 30 nm to 300 nm. The particle size distribution is not specifically limited and may be, for example, less than or equal to 50% of the average value of the particle diameter.

Preparation of Lithium Secondary Battery

In the present invention, a cathode active material including the lithium iron phosphate nanopowder having the olivine crystal structure may be provided. The cathode active material may selectively further include a conductive agent, a binder and a filler other than the lithium iron phosphate powder.

The conductive agent may include any material having conductivity and not inducing a chemical change in a battery without specific limitation, and may include, for example, graphite such as natural graphite and synthetic graphite; carbon blacks such as carbon black, acetylene black, ketchen black, channel black, furnace black, lamp black, and thermal black; conductive fibers such as a carbon fiber and a metal fiber; metal powders such as a carbon fluoride powder, an aluminum powder and a nickel powder; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; and conductive materials such as a polyphenylene derivative. Generally, the conductive agent may be included by 1 wt % to 30 wt % based on the total amount of a mixture including the cathode active material.

The binder may be any component that assists the bonding of the active material and the conductive agent and the bonding with a current collector without specific limitation, and may include, for example, polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene monomer (EPDM), sulfonated EPDM, a styrene butadiene rubber, a fluorine rubber, various copolymers, etc.

Generally, the binder may be included by 1 wt % to 30 wt % based on the total amount of a mixture including the cathode active material.

The filler is a component suppressing the expansion of an electrode and may be selectively used. The filler may be any fibrous material that may not induce a chemical change in the battery, without specific limitation, and may include, for example, an olefin-based polymer such as polyethylene and polypropylene; and a fibrous material such as a glass fiber and a carbon fiber.

In addition, in an embodiment of the present invention, a cathode for a lithium secondary battery obtained by coating the cathode active material on a current collector is provided.

The cathode for the lithium secondary battery may be fabricated by, for example, dissolving the cathode active material in a solvent to prepare a slurry, coating the slurry on the current collector, drying and pressing.

The current collector of the cathode may be any material having conductivity and not inducing chemical change of the battery, without specific limitation, and may include, for example, stainless steel; aluminum; nickel; titanium; calcined carbon; or a surface treated material of the aluminum or the stainless steel with carbon, nickel, titanium, silver, etc.

Generally, the current collector may have a thickness of 3 to 500 μm, and minute embossing may be formed on the surface of the current collector to increase the adhesiveness of the cathode active material. Various shapes such as a film, a sheet, a foil, a net, a porous material, a foamed material, a non-woven fabric, etc. may be used as the current collector.

In addition, in an embodiment of the present invention, a lithium secondary battery including a cathode including the cathode active material, an anode, a separator and a non-aqueous electrolyte containing a lithium salt may be provided.

The anode may be fabricated by, for example, coating an anode mixture including an anode active material on an anode current collector, and drying. In the anode mixture, the above-described components such as the conductive agent, the binder and the filler may be included as occasion demands.

The anode current collector may be any material having high conductivity and not inducing the chemical change of the battery, without specific limitation, and may include, for example, copper; stainless steel; aluminum; nickel; calcined carbon; a surface treated material of copper or stainless steel with carbon, nickel, titanium, silver, etc; and an alloy of aluminum-cadmium.

Meanwhile, the current collector may have the thickness of 3 to 500 μm, and minute embossing may be formed on the surface of the current collector to increase the adhesiveness of the anode active material as in the cathode current collector. Various shapes such as a film, a sheet, a foil, a net, a porous material, a foamed material, a non-woven fabric, etc. may be used as the current collector.

The separator is disposed between the cathode and the anode, and an insulating thin film having high ion transmittance and high mechanical strength may be used.

The pore diameter of the separator may be generally from 0.01 μm to 10 μm, and the thickness thereof may be generally from 5 μm to 300 μm.

The separator may include a chemical resistant and hydrophobic olefin-based polymer such as polypropylene; a sheet or a non-woven fabric formed by using a glass fiber or polyethylene, etc.

When a solid electrolyte such as a polymer is used as the electrolyte, the solid electrolyte may also play the role of the separator.

The non-aqueous electrolyte containing the lithium salt includes the electrolyte and the lithium salt, and the electrolyte may include a non-aqueous organic solvent or an organic solid electrolyte.

The non-aqueous organic solvent may include, for example, aprotic organic solvents such as N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butyrolactone, 1,2-dimethoxyethane, tetrahydroxyfuran, 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphoric acid triester, trimethoxymethane, dioxolane derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, ether, methyl propionate, ethyl propionate, etc.

The organic solid electrolyte may include, for example, polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, a phosphoric acid ester polymer, poly agitation lysine, polyester sulfide, polyvinyl alcohol, polyvinylidene fluoride, and a polymer containing an ionic dissociable group.

The lithium salt may include a material favorably soluble in the non-aqueous electrolyte such as LiCl, LiBr, LiI, LiClO₄, LiBF₄, LiB₁₀C₁₀, LiPF₆, LiCF₃SO₃, LiCF₃CO₂, LiAsF₆, LiSbF₆, LiAlCl₄, CH₃SO₃Li, CF₃SO₃Li, (CF₃SO₂)₂NLi, chloroborane lithium, a low molecular weight aliphatic lithium carbonate, lithium 4-phenylborate, imide, etc.

In addition, the electrolyte may further include (for improving charge and discharge properties, and flame retardance, etc.), for example, pyridine, triethyl phosphite, triethanolamine, a cyclic ether, ethylenediamine, n-glyme, hexaphosphoric acid amide, nitrobenzene derivatives, sulfur, a quinone imine dye, N-substituted oxazolidinone, N,N-substituted imidazolidine, an ethylene glycol dialkyl ether, an ammonium salt, pyrrole, 2-methoxyethanol, trichloro aluminum, etc. A halogen-containing solvent such as carbon tetrachloride, trifluoroethylene, etc. may be further included to impart incombustibility, and a carbon dioxide gas may be further included to improve preservation properties at a high temperature.

As described above, the method for preparing the lithium iron phosphate nanopowder of the present invention may be performed at relatively lower pressure conditions when compared to a common hydrothermal synthesis method or a supercritical hydrothermal synthesis method by using a glycothermal synthesis method that is a liquid-state reaction method and by using a novel glycerol reaction solvent. In addition, the particle size and the particle size distribution of the lithium iron phosphate nanopowder may be effectively controlled when compared to the common glycothermal synthesis method. Further, the safety and economical feasibility of the method may be secured according to the preparation method of the present invention. A lithium secondary battery including the lithium iron phosphate nanopowder thus prepared as a cathode active material may have good capacity and stability.

EXAMPLE

An example embodiment of the invention will be described below in more detail. The present invention may, however, be embodied in different forms and should not be construed as limited to the embodiment set forth herein. Rather, the embodiment is provided so that this disclosure will be thorough and complete, and will fully convey the scope of the inventive concept to those skilled in the art.

Example 1

0.42 g of lithium hydroxide hydrate (LiOH.H₂O), 2.45 g of ferric citrate hydrate (FeC₆H₅O₇.nH₂O) and 0.98 g of phosphoric acid (H₃PO₄) were added in 50 ml of glycerol and sufficiently stirred to prepare a mixture solution.

The sufficiently stirred mixture solution was put into a 100 ml autoclave and a reaction was performed at 180° C. for 18 hours.

After finishing the reaction, the remaining reactant was cooled and washed sequentially using acetone and methanol.

After washing, the product was dried using a vacuum drier.

After finishing the washing and drying, the reaction product thus obtained was analyzed with an X-ray diffraction spectroscopy and a scanning electron microscope. The reaction product was confirmed to be a lithium iron phosphate nanopowder having a particle size of 50 nm to 100 nm and having a pure olivine crystal structure (See FIGS. 1 and 2).

As shown through the example, the lithium iron phosphate nanopowder prepared by the method of the present invention has small and uniform particle size and good particle size distribution properties. 

What is claimed is:
 1. A method for preparing a lithium iron phosphate nanopowder, comprising the steps of: (a) preparing a mixture solution by adding a lithium precursor, an iron precursor and a phosphorus precursor in a glycerol solvent; and (b) putting the mixture solution into a reactor and heating to prepare the lithium iron phosphate nanopowder under pressure conditions of 10 bar to 100 bar.
 2. The method for preparing a lithium iron phosphate nanopowder of claim 1, further comprising the step of (c) heat treating the lithium iron phosphate nanopowder thus prepared to form a coating layer at a portion or a whole of a surface of an individual particle of the nanopowder.
 3. The method for preparing a lithium iron phosphate nanopowder of claim 1, wherein the lithium iron phosphate nanopowder prepared in Step (b) is sequentially sequentially conducted a washing step and a drying step.
 4. The method for preparing a lithium iron phosphate nanopowder of claim 1, wherein Step (b) is performed at a temperature less than or equal to a boiling point of the glycerol solvent.
 5. The method for preparing a lithium iron phosphate nanopowder of claim 1, wherein Step (b) is performed at a temperature range of 150° C. to 290° C.
 6. The method for preparing a lithium iron phosphate nanopowder of claim 1, wherein Step (b) is performed for 1 to 48 hours.
 7. The method for preparing a lithium iron phosphate nanopowder of claim 1, wherein the lithium precursor is at least one selected from the group consisting of lithium acetate dihydrate (CH₃COOLi.2H₂O), lithium hydroxide monohydrate (LiOH.H₂O), lithium hydroxide (LiOH), lithium carbonate (Li₂CO₃), lithium phosphate (Li₃PO₄), lithium phosphate dodecahydrate (Li₃PO₄.12H₂O) and lithium oxalate (Li₂C₂O₄), or a mixture thereof.
 8. The method for preparing a lithium iron phosphate nanopowder of claim 1, wherein the iron precursor is at least one selected from the group consisting of iron citrate (FeC₆H₅O₇), iron citrate hydrate (FeC₆H₅O₇.nH₂O), ferrous sulfate heptahydrate (FeSO₄.7H₂O), iron(II) oxalate dihydrate (FeC₂O₄.2H₂O), iron acetyl acetonate (Fe(C₅H₇O₂)₃), iron phosphate dihydrate (FePO₄.2H₂O), ferric hydroxide (FeO(OH)), and a mixture thereof.
 9. The method for preparing a lithium iron phosphate nanopowder of claim 1, wherein the phosphorus precursor is at least one selected from the group consisting of tri-ammonium phosphate trihydrate ((NH₄)₃PO₄.3H₂O), ammonium phosphate ((NH₄)₂HPO₄), ammonium dihydrogen phosphate (NH₄H₂PO₄) phosphoric acid (H₃PO₄), and a mixture thereof.
 10. The method for preparing a lithium iron phosphate nanopowder of claim 2, wherein the heat treating is performed by heating to a temperature range of 400° C. to 900° C.
 11. The method for preparing a lithium iron phosphate nanopowder of claim 3, wherein the drying is performed at 20° C. to 160° C. for 2 to 40 hours.
 12. A lithium iron phosphate nanopowder comprising the lithium iron phosphate nanopowder prepared according to claim 1 and having an olivine crystal structure.
 13. The lithium iron phosphate nanopowder of claim 12, wherein a particle diameter of the lithium iron phosphate nanopowder is from 30 nm to 300 nm.
 14. The lithium iron phosphate nanopowder of claim 12, wherein a particle size distribution of the lithium iron phosphate nanopowder is less than or equal to 50% of an average value of the particle diameter.
 15. The lithium iron phosphate nanopowder of claim 12, further comprising a carbon coating layer or a glassy lithium compound coating layer on a surface of a particle of the lithium iron phosphate nanopowder.
 16. The lithium iron phosphate nanopowder of claim 15, wherein a thickness of the coating layer is less than or equal to 10 nm.
 17. A cathode active material comprising the lithium iron phosphate nanopowder according to claim
 12. 18. The cathode active material of claim 17, further comprising a conductive agent, a binder and a filler.
 19. A cathode for a lithium secondary battery comprising the cathode active material of claim
 17. 20. A lithium secondary battery comprising the cathode of claim 19, an anode, a separator and a non-aqueous electrolyte comprising a lithium salt. 